The aim of this work was the synthesis and characterization of new thiophenolate chelate complexes with an amidine function of the general formula M(SC6H4[2–N=CH–NR2])2 employing the group 12 metals zinc, cadmium and mercury. Two different synthesis routes were used. In the first reaction pathway, metal cations and secondary amines cause a ring opening reaction of the heterocycle benzothiazole that results in the formation of thiophenolate chelate complexes. The structural composition of the formed complexes was determined by X–ray crystallography, and NMR spectroscopy clarified the mechanism of these reactions. Dynamic NMR spectroscopy delivered thermodynamic data arising from the hindered rotation about the C–N single bond of the amidine group. In addition further divalent 4th row transition metal acetates were probed to investigate their reactivity towards benzothiazole and secondary amines. The use of nickel acetate in the reactions yielded thiophenolate chelate complexes, whereas in the reactions with cobalt acetate an oxidation of benzothiazoline intermediates occurred which resulted in the formation of disulfides. Only traces of cobalt containing thiophenolate chelate complexes were detected by mass spectrometry. The use of copper(II) acetate monohydrate formed tetra-μ-acetato-bis[benzothiazolecoper(II)]. Furthermore, the thiophenolate complexes were synthesized by reacting bis(2– aminothiophenolate)metal chelates with dimethylformamide dimethylacetal. Zinc and mercury thiophenolate chelate complexes as well as a metal-free disulfide were characterized by X–ray crystallography. The hindered rotation about the C–N single bond of the amidine group in these complexes was investigated using dynamic NMR spectroscopy.